CN106479133A - A kind of scratch-resistant composite and preparation method thereof - Google Patents
A kind of scratch-resistant composite and preparation method thereof Download PDFInfo
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- CN106479133A CN106479133A CN201510530226.7A CN201510530226A CN106479133A CN 106479133 A CN106479133 A CN 106479133A CN 201510530226 A CN201510530226 A CN 201510530226A CN 106479133 A CN106479133 A CN 106479133A
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Abstract
The present invention provides a kind of scratch-resistant composite and preparation method thereof, and it is by 100 parts of plastic resin, tetragonal crystal system z BC25 30 parts of N, 0.1 2 parts of coupling agent and 0.1 2 parts of processing aid blended, extrusion form.The present invention uses novel superhard material z BC2N, as scratch-resistant modified filler, makes the scratch-resistant composite of preparation have high scraping and wiping resistance performance, and than traditional B4C or polytetrafluoroethylmodified modified scraping and wiping resistance performance is more preferably it is adaptable to the field such as automobile, electric, building, space flight.
Description
Technical field
The present invention relates to a kind of material modified technical field is and in particular to a kind of scratch-resistant material and preparation method thereof.
Background technology
Plastics are widely used at present, and such as polypropylene is just widely used in the fields such as inner and outer decorative parts of automobile, electronic product.But plastics all generally have a defect at present it is simply that the scratch resistance of itself is poor, and the surface of product easily scratches, thus reducing the appearance looks elegant degree of product, and the cut in product surface product also results in its stress concentration, limits its serviceability.Particularly the scratch resistance with talc plastics is worse, and material is in pressing-in force and sliding force or horizontal stroke（Side）Surrendering in the presence of power, producing ductility/brittle break thus causing scratch.In scratch, uneven surface produces uneven light scattering and " scratch turns white ", thus limiting use at the higher parts of scraping and wiping resistance performance requirement for the plastics.
In order to solve this problem, generally add scratch resistance liniment in the plastic to improve its scratch-resistant effect, but traditional scratch resistance liniment is mainly erucyl amide class material and high silicones, this two classes material exist in itself abnormal smells from the patient heavier the shortcomings of, had a strong impact on its range of application.
BC2N is a kind of diamond-like, and its hardness is only second to diamond, and has and compare boron nitride（BN）Higher volume and shear elasticity modulus.So BC2N has the advantages that diamond and BN both materials, and it has very big potential in application, also result in the attention of international material circle.And tetragonal crystal system
z-BC2N is a kind of novel superhard material, and its mechanical stability is good, and hardness is up to 77GPa, the c-BN being 60 far above the hardness as scratch-resistant modified filler for the tradition, is that to have now been found that is the material the hardest under diamond.But less to its application at present, and even more not yet report as the scratch-resistant modified filler of plastics.
Content of the invention
It is an object of the invention to provide a kind of scratch-resistant composite and preparation method thereof.
Technical scheme is as follows：
A kind of scratch-resistant composite, is prepared from by weight by following components：
100 parts of plastic resin
Tetragonal crystal system z-BC2N 5-30 part
Coupling agent 0.1-2 part
Processing aid 0.1-2 part.
Scheme further, described plastic resin is at least one in polyethylene, polypropylene, polyamide, polyester, polyphenylene sulfide, polyether-ether-ketone and polyimides.
Described polyamide is polyamide 6, polyamide 66, polyamide 610 and polyamide 1010
In at least one.
Described polyester is polyethylene terephthalate, PTT（PET）, at least one in polybutylene terephthalate (PBT) and Merlon.
Described tetragonal crystal system z-BC2The particle diameter of N is 1500 mesh -5000 mesh.
Described coupling agent is at least one in silane coupler, titanate coupling agent and rare earth aluminic acid ester coupling agent.
Described silane coupler is 3- aminopropyl triethoxysilane（KH550）；Titanate coupling agent is sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester（NDZ-102）；Rare earth aluminic acid ester coupling agent is aluminic acid three isopropyl ester（DL-411）.
Described processing aid is silicone powder and N, N '-ethylene bis stearamide（EBS）One of or two kinds of mixture.
Another goal of the invention of the present invention is the preparation method providing above-mentioned scratch-resistant composite, and step is as follows：
（1）100 parts of plastic resins are added together with 0.1-2 part coupling agent speed be 100-300 turn/the room temperature high-speed mixer of min mixed；Add 5-30 part tetragonal crystal system z-BC2N continues mixing；It is eventually adding 0.1-2 part processing aid and continues mixing, total incorporation time is 2-8min；
（2）Feed the mixture into carry out in extruder melting, extrude, cool down, being dried, pelletizing obtains scratch-resistant composite；Wherein extruder each area temperature is 140-355 DEG C, and extrusion screw rod draw ratio is 30-40, and extrusion screw rod rotating speed turns/min for 150-350.
So the present invention compared with prior art has the advantage that：
1st, the present invention uses novel superhard material tetragonal crystal system z-BC2N as modifying plastics scratch resistance liniment, due to tetragonal crystal system z-BC2Hardness more traditional scratch resistance liniment of N is high, after plastic resin is modified, can improve the scraping and wiping resistance performance of composite wood；
2nd, the present invention has carried out tetragonal crystal system z-BC2N is as the new opplication of modifying plastics scratch resistance liniment；
3rd, the scratch-resistant composite of present invention preparation, has good scraping and wiping resistance performance, and can be applicable to the fields higher to scraping and wiping resistance performance requirement such as automobile, electric, building, space flight.
Specific embodiment
Embodiment 1
By 100 parts of polypropylene and 0.05
Part KH550,0.05 part of NDZ-102 add rotating speed to carry out room temperature mixing for 100 turns/min high-speed mixer；Add the tetragonal crystal system z-BC that 5 parts of particle diameters are 1500 mesh2N continues mixing；It is eventually adding 0.1 part of silicone powder and continue mixing；Total incorporation time is 2min；
Mixed blend is obtained scratch-resistant composite by double screw extruder extruding pelletization；Each area temperature of wherein extruder is followed successively by 140 DEG C, 160 DEG C, 160 DEG C, 170 DEG C, 170 DEG C, 180 DEG C, 180 DEG C, 190 DEG C, 190 DEG C, 195 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 30, and extrusion screw rod rotating speed is 150 revs/min.
Embodiment 2
2 parts of DL-411 are added to mix through high-speed mixer room temperature in 100 weight portion PP, again the z-BC2N that 30 parts of particle diameters are 2500 mesh is added thereto and carries out room temperature mixed at high speed, finally 1 part of silicone powder, 1 part of EBS addition are carried out room temperature mixed at high speed, in whole mixed process, mixing velocity is 300 turns/min, and incorporation time overall length is
8min ；
Mixed blend is obtained scratch-resistant composite by double screw extruder extruding pelletization；Each area temperature of wherein extruder is followed successively by 140 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 215 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 350 revs/min.
Embodiment 3
In 100 weight portion PET
Middle add 1 part of KH550 to mix through high-speed mixer room temperature, then the z-BC that 20 parts of particle diameters are 5000 mesh2N
It is added thereto and carries out room temperature mixed at high speed, finally 0.5 part of silicone powder, 1 part of EBS addition are carried out room temperature mixed at high speed, in whole mixed process, mixing velocity is 250 turns/min, and incorporation time is 4min；
Mixed blend is obtained scratch-resistant composite by double screw extruder extruding pelletization；Each area temperature of wherein extruder is followed successively by 240 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 290 DEG C, 290 DEG C, 290 DEG C, 290 DEG C, 295 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 35, and extrusion screw rod rotating speed is 300 revs/min.
Embodiment 4
In 100 weight portions
0.5 part of NDZ-102 and 0.2 part of DL-411 is added to mix through high-speed mixer room temperature in PA66, then the z-BC that 30 parts of particle diameters are 2500 mesh2N is added thereto and carries out room temperature mixed at high speed, finally 0.5 part of silicone powder, 1 part of EBS addition is carried out room temperature mixed at high speed, in whole mixed process, mixing velocity is 150 turns/min, and incorporation time is 6min；
Mixed blend is passed through double screw extruder extruding pelletization, each area temperature of extruder is followed successively by 220 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, 290 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 35, and extrusion screw rod rotating speed is 320 revs/min.
Embodiment 5
0.5 part of NDZ-102 and 0.2 is added in 100 weight portion PC
Part DL-411 mixes through high-speed mixer room temperature, then the z-BC that 6 parts of particle diameters are 1500 mesh2N is added thereto and carries out room temperature mixed at high speed, finally adds 1.2 parts of EBS and carries out room temperature mixed at high speed, in whole mixed process, mixing velocity is 180 turns/min, and incorporation time is 6min
；
Mixed blend is obtained scratch-resistant composite by double screw extruder extruding pelletization；Each area temperature of wherein extruder is followed successively by 240 DEG C, 260 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 290 DEG C, 295 DEG C, 300 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 35, and extrusion screw rod rotating speed is 280 revs/min.
Embodiment 6
In 100 weight portion PPS
Middle 0.3 part of NDZ-102 and 0.2 part of DL-411 of addition mixes through high-speed mixer room temperature, then 8 parts of particle diameters are 5000 mesh z-BC2N is added thereto and carries out room temperature mixed at high speed, finally adds 0.8 part of silicone powder and carries out room temperature mixed at high speed, in whole mixed process, mixing velocity is 220 turns/min, and incorporation time is 7.5min；
Mixed blend is obtained scratch-resistant composite by double screw extruder extruding pelletization；Each area temperature of wherein extruder is followed successively by 260 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 290 DEG C, 290 DEG C, 290 DEG C, 290 DEG C, 295 DEG C, 300 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 35, and extrusion screw rod rotating speed is 340 revs/min.
Embodiment 7
In 100 weight portions
Add 0.3 part of NDZ-102 and 0.4 part of KH550 to mix through high-speed mixer room temperature in PEEK, then 15 parts of particle diameters are 5000 mesh z-BC2N
It is added thereto and carries out room temperature mixed at high speed, finally 0.7 part of silicone powder, 0.5 part of EBS addition are carried out room temperature mixed at high speed, in whole mixed process, mixing velocity is 220 turns/min, and incorporation time is 7.5min；
Mixed blend is obtained scratch-resistant composite by double screw extruder extruding pelletization；Each area temperature of wherein extruder is followed successively by 280 DEG C, 290 DEG C, 300 DEG C, 320 DEG C, 340 DEG C, 340 DEG C, 350 DEG C, 350 DEG C, 355 DEG C, 355 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 35, and extrusion screw rod rotating speed is 340 revs/min.
Embodiment 8
In 100 weight portion PA6
Middle add 0.5 part of NDZ-102 and 0.2 part of DL-411 to mix through high-speed mixer room temperature, then the z-BC that 12 parts of particle diameters are 2500 mesh2N
It is added thereto and carries out room temperature mixed at high speed, finally 0.5 part of silicone powder, 1 part of EBS addition are carried out room temperature mixed at high speed, in whole mixed process, mixing velocity is 150 turns/min, and incorporation time is 6min；
Mixed blend is obtained scratch-resistant composite by double screw extruder extruding pelletization；Each area temperature of wherein extruder is followed successively by 160 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 235 DEG C, 240 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 35, and extrusion screw rod rotating speed is 320 revs/min.
Embodiment 9
In 100 weight portion PA6
Middle add 0.5 part of NDZ-102 and 0.2 part of DL-411 to mix through high-speed mixer room temperature, then the z-BC that 12 parts of particle diameters are 2500 mesh2N is added thereto and carries out room temperature mixed at high speed, finally 0.5 part of silicone powder, 1 part of EBS addition is carried out room temperature mixed at high speed, in whole mixed process, mixing velocity is 150 turns/min, and incorporation time is
6min；
Mixed blend is obtained scratch-resistant composite by double screw extruder extruding pelletization；Each area temperature of wherein extruder is followed successively by 160 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 235 DEG C, 240 DEG C from feeding section to head temperature, extrusion screw rod draw ratio is 35, and extrusion screw rod rotating speed is 320 revs/min.
Comparative example 1
Pure HOPP material.
Comparative example 2
Prepare comparative example 2 by component and the preparation method of embodiment 1, its differ only in by embodiment 1 " 5 parts of particle diameters are the tetragonal crystal system z-BC of 1500 mesh2N " is changed to " 4% erucyl amide ".
Comparative example 3
Prepare comparative example 2 by component and the preparation method of embodiment 1, its differ only in by embodiment 1 " 5 parts of particle diameters are the tetragonal crystal system z-BC of 1500 mesh2N " is changed to " 4% silicone ".
The scratch-resistant composite of above-described embodiment 1-9 and the preparation of comparative example 1-3 is molded into batten with single screw rod respectively, then detects its scraping and wiping resistance performance respectively, be specifically shown in Table 1.The temperature of wherein single screw rod injection is followed successively by 210 DEG C, 225 DEG C, 225 DEG C, 230 DEG C, 230 DEG C from feeding to head, and screw in injection molding machine draw ratio is 35, and screw speed is 320 turns/min, and injection pressure is
60MPa, screw back pressure is 8MPa, and injection time is 8s, and cool time is 6s.
Scratch-resistant test is tested by PV3952, and load is 10N, by measuring the Δ L-value of scraping specimen surface
(i.e. the change flag of black-white colors) passing judgment on its scraping and wiping resistance performance, the numerical value of Δ L is less, represents that the scraping and wiping resistance performance of material is better.
Table 1：Scraping and wiping resistance performance
| ΔL | Coefficient of friction（Dry grinding） | Abrasion/mg（Dry grinding） | |
| Comparative example 1 | 3.34 | 0.33 | 11.2 |
| Comparative example 2 | 1.46 | 0.28 | 10.8 |
| Comparative example 3 | 1.81 | 0.21 | 10.5 |
| Embodiment 1 | 0.88 | 0.12 | 6.4 |
| Embodiment 2 | 0.68 | 0.09 | 1.9 |
| Embodiment 3 | 0.93 | 0.07 | 3.2 |
| Embodiment 4 | 1.07 | 0.06 | 2.8 |
| Embodiment 5 | 0.68 | 0.12 | 4.5 |
| Embodiment 6 | 1.17 | 0.1 | 3.1 |
| Embodiment 7 | 1.09 | 0.04 | 2.2 |
| Embodiment 8 | 0.67 | 0.08 | 0.03 |
| Embodiment 9 | 0.83 | 2.7 | 2.5 |
As can be seen from Table 1, the scraping and wiping resistance performance of the scratch-resistant composite of present invention preparation is all significantly better than comparative example 1-3, so the scratch-resistant composite of the present invention has excellent wear-resisting, scraping and wiping resistance performance.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.Person skilled in the art obviously easily can make various modifications to these embodiments, and General Principle described herein is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to embodiment here, according to the announcement of the present invention, the improvement made without departing from scope and modification all should be within protection scope of the present invention for those skilled in the art.
Claims (9)
1. a kind of scratch-resistant composite it is characterised in that：It is prepared from by weight by following components
：
Plastic resin
100 parts
Tetragonal crystal system z-BC2N 5-30 part
Coupling agent
0.1-2 part
Processing aid
0.1-2 part.
2. the scratch-resistant composite according to claim 1 it is characterised in that：Described plastic resin is at least one in polyethylene, polypropylene, polyamide, polyester, polyphenylene sulfide, polyether-ether-ketone and polyimides.
3. scratch-resistant composite according to claim 2 it is characterised in that：Described polyamide is polyamide 6, polyamide 66, polyamide 610 and polyamide 1010
In at least one.
4. the scratch-resistant composite according to claim 2 it is characterised in that：Described polyester is at least one in polyethylene terephthalate, PTT, polybutylene terephthalate (PBT) and Merlon.
5. scratch-resistant composite according to claim 1 it is characterised in that：Described tetragonal crystal system z-BC2The particle diameter of N is 1500 mesh -5000 mesh.
6. the scratch-resistant composite according to claim 1 it is characterised in that：Described coupling agent is at least one in silane coupler, titanate coupling agent and rare earth aluminic acid ester coupling agent.
7. scratch-resistant composite according to claim 6 it is characterised in that：Described silane coupler is 3- aminopropyl triethoxysilane；Titanate coupling agent is sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester；Rare earth aluminic acid ester coupling agent is aluminic acid three isopropyl ester.
8. the scratch-resistant composite according to claim 1 it is characterised in that：Described processing aid is silicone powder and N, one of N '-ethylene bis stearamide or two kinds of mixture.
9. the scratch-resistant composite as any one of claim 1-8 preparation method it is characterised in that：Step is as follows：
（1）100 parts of plastic resins are added together with 0.1-2 part coupling agent speed be 100-300 turn/the room temperature high-speed mixer of min mixed；Add 5-30 part tetragonal crystal system z-BC2N continues mixing；It is eventually adding 0.1-2 part processing aid and continues mixing, total incorporation time is 2-8min；
（2）Feed the mixture into carry out in extruder melting, extrude, cool down, being dried, pelletizing obtains scratch-resistant composite；Wherein extruder each area temperature is 140-355 DEG C, and extrusion screw rod draw ratio is 30-40, and extrusion screw rod rotating speed turns/min for 150-350.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141609A (en) * | 2017-06-30 | 2017-09-08 | 吉林恒辉新材料有限公司 | A kind of scratch-resistant PP composite material and preparation method thereof |
| CN108219401A (en) * | 2018-03-21 | 2018-06-29 | 安徽江淮汽车集团股份有限公司 | A kind of flame-proof abrasion-resistant PET composite material and preparation method thereof |
| CN115181408A (en) * | 2022-08-17 | 2022-10-14 | 浙江普山新材料科技有限公司 | Wear-resistant PC resin material and preparation method thereof |
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2015
- 2015-08-27 CN CN201510530226.7A patent/CN106479133A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103044753A (en) * | 2013-01-16 | 2013-04-17 | 合肥杰事杰新材料股份有限公司 | Abrasion-resistant composite material and preparation method thereof |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141609A (en) * | 2017-06-30 | 2017-09-08 | 吉林恒辉新材料有限公司 | A kind of scratch-resistant PP composite material and preparation method thereof |
| CN108219401A (en) * | 2018-03-21 | 2018-06-29 | 安徽江淮汽车集团股份有限公司 | A kind of flame-proof abrasion-resistant PET composite material and preparation method thereof |
| CN115181408A (en) * | 2022-08-17 | 2022-10-14 | 浙江普山新材料科技有限公司 | Wear-resistant PC resin material and preparation method thereof |
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